Oil- and water-repellent fluorine-containing compositions

ABSTRACT

THE OLEOPHOBIC AND HYDROPHOBIC PROPERTIES OF POLYMERS OF HIGHLY FIUORINATED MONOMERS THE FIUORINATED PARTS OF WHOSE MOLECULES ARE BRANCHES ARE INCREASED BY MIXING THE POLYMERS WITH OLEOPHOBIC AND HYDROPHOBIC POLYMERS OF HIGHLY FLUORINATED MONOMERS WHOSE FLUORINATED PARTS HAVE LINEAR STRUCTURES; PEFERRED MIXTURES COMPRISE 0.50% TO 15% OF THE LATTER AND 85% TO 99.5% OF THE FORMER. IMPROVED SOLUBILITY OF THE MIXTURES IN HALOGENATED SOLVENTS IS GIVEN BY CO-POLYMERISING THE MONOMERS WITH POLYMERISABLE VINYL COMPOUNDS NOT CONTAINING FLUORINE, FOR EXAMPLE BUTYL METHACRYLATE. SOLUTIONS IN SUCH SOLVENTS CAN BE APPLIED TO TEXTILES TO IMPART OLEOPHOBIC AND HYDROPHOBIC PROPERTIES. RESISTANCE TO DRY-CLEANING AND LAUDERIN OF TREATED FABRICS CAN BE IMPROVED BY INTRODUCING INTO THE COPOLYMERISATION SYSTERMS MINOR PROPORTIONS OF MONOMRS ABLE TO INTRODUCE CROSS-LINKING SITES, FOR EXAMPLE HYDROXYETHYL METHACRYLATE, AND SUBSEQUENTLY CURING BY HEATING THE TREATED FABRIC. PREFERRED LINEAR MOLECULES ARE 1H,1H-PENTADECAFLUOROOCTYL ACRYLATE AND THE REACTION PRODUCT OF POLY(VINYL ALCOHOL) AND PERFLUOROOCTANOIC AICD; PREFERRED BRANCHED MOLEUCLES ARE (I) THE METACRYLIC ESTER,   C10F19OC6H4CH2O2CC(CH3)=CH2   OF THE TETRAFLUOROETHYLENE PENTAMER DERIVATIVE OF P-HYDROXYBENZYL ALCOHOL, (II) THE VINYL ESTER   C10F19OC6H4CO2CH=CH2   OF THE TETRAFLUOROETHYLENE PENTAMER DERIVATIVE OF P-HYDROXYBENZOIC ACID AND (III) THE VINYL ESTER   (C2F5)2(CF3)CCH2CO2CH=CH2   OF TRIDECAFLUORO-2-METHYL-2-ETHYL-1H,1H-BUTANE-1-CARBOXYLIC ACID.

3,595,944 OIL- AND WATER-REPELLENT FLUORINE- CONTAINING COMPOSITIONS George Hall Manning and Samuel John Webster, Runcorn, England, assignors to Imperial Chemical Industries Limited, London, England No Drawing. Filed Apr. 1, 1968, Ser. No. 717,908 Claims priority, application Great Britain, Aug. 24, 1967, 18,777/67 Int. Cl. C08f 29/22 U.S. Cl. 260-900 11 Claims ABSTRACT OF THE DISCLOSURE The oleophobic and hydrophobic properties of polymers of highly fluorinated monomers the fluorinated parts of whose molecules are branched are increased by mixing the polymers with oleophobic and hydrophobic polymers of highly fluorinated monomers whose fluorinated parts have linear structures; preferred mixtures comprise 0% to 15% of the latter and 85% to 99.5% of the former. Improved solubility of the mixtures in halogenated solvents is given by co-polymerising the monomers with polymerisable vinyl compounds not containing fluorine, for example butyl methacrylate.

Solutions in such solvents can be applied to textiles to impart oleophobic and hydrophobic properties. Resistance to dry-cleaning and laundering of treated fabrics can be improved by introducing into the copolymerisation systems minor proportions of monomers able to introduce cross-linking sites, for example hydroxyethyl methacrylate, and subsequently curing by heating the treated fabric.

Preferred linear molecules are 1H,lH-pentadecafluorooctyl acrylate and the reaction product of poly(vinyl alcohol) and perfluorooctanoic acid; preferred branched molecules are (i) the methacrylic ester,

C1OF1QOCGH4CH202CC 1:01-12 of the tetrafluoroethylene pentamer derivative of p-hydroxybenzyl alcohol, (ii) the vinyl ester of the tetrafiuoroethylene pentamer derivative of p-hydroxybenzoic acid and (iii) the vinyl ester C F CF CCH CO CH=CH of tridecafluoro-2-methyl-2-ethyl-1H,lH-butane-l-carboxylic acid.

This invention relates to compositions that are mixtures of fluorine-containing organic compounds and possess the property of oiland Water-repellency, and are useful for treating materials such as textiles, leather, paper, and rubber both natural and synthetic in order to impart this property to them.

Some fluorine-containing organic polymers derived from highly fluorinated monomers in which the fluorinated part of the molecule is linear, or contains at the most a small degree of branching, are known to possess oiland water-repelling properties. Also known are polymers derived from highly fluorinated monomers in which the fluorine-containing part is highly branched. Comparative tests show that those polymers having a predominantly linear structure in the highly fluorinated parts of their molecules are usually superior to those having highly branched structures in oiland water-repelling formulations suitable for application to textiles, leather and paper.

We have now found that mixtures of these two types of fluorine-containing polymers possess unexpectedly high degrees of oiland water-repellency in relation to the amount present of the polymer derived from the substantially linear monomer.

United States Patent O Thus the invention in its general form provides novel compositions possessing oiland water-repelling properties comprising mixtures of at least one fluorine-containing organic polymer of a highly fluorinated monomer in which the fluorinated part of the molecule is linear or only slightly branched, and at least one fluorine-containing organic polymer of a highly fluorinated monomer in which the fluorinated part of the molecule is highly branched.

Within the scope of this specification the term polymer also includes copolymers of the monomers whose fluorinated parts of the molecule are highly branched, and also copolymers of the monomers whose fluorinated parts are predominantly linear. This comes about because in the application of oiland water-repelling finishes to textiles and other materials it is convenient to apply the formulation as a solution in water or in a chlorinated solvent, for example, 1,1,l-trichloroethane, and the solubility of the novel compositions in such solvents can be much increased by the presence of a proportion in the copolymer between the fluorinated monomer and a non-fluorine containing monomer, for example alkyl methacrylates, acrylates and vinyl esters of which butyl methacrylate is particularly suitable.

Also within the scope of the invention is the incorporation in the co-polymers of minor proportions of monomers containing cross-linking sites in their molecules, for example hydroxyethyl methacrylate, methylol acrylamide and glycidyl methacrylate. Cross-linking occurring during subsequent curing operations on textiles treated with oiland water-repelling compositions confers resistance to dry-cleaning and laundering processes. Toluylene diisocyanate is a convenient cross-linking agent for compositions containing hydroxyethyl methacrylate, and chloracetic acid for those containing methylol acrylamide.

The invention also comprises a method of imparting oiland water-repelling properties to textiles, yarns, threads, felts, leather, paper, rubber both natural and synthetic, plastic materials, glass and ceramics by treating them with the novel compositions, and it also comprises these various materials when rendered oiland water-repellent by said treatment.

The proportion in the compositions of the polymer of the monomer whose fluorinated part is linear or only slightly branched is conveniently from 1% to 25% by weight of the composition, but it may be less than 1% or greater than 25%. Particularly suitable proportions are from 0.50% to 15%.

Among fluorinated monomers in which the fluorinebearing part is highly branched and which yield polymers suitable for the compositions of the invention are polymerizable or polymeric derivatives of branched-chain, internally unsaturated oligomers of perfiuoroolefins or of degradation products of such oligomers; polymerisable derivatives of fluorine-containing tertiary and secondary alcohols and ketones. Examples of these monomers are polymerisable derivatives of oligomers of tetrafluoroethylene such as those containing acrylic groups, for example the acrylic ester,

and the corresponding methacrylic ester of the tetrafiuoroethylene pentarner derivative C F OC H CH OH; the acrylic ester of the derivative C F OCH CH OI-I; and the vinyl ester, C F OC H CO CH=CH of the derivative C F OC H COOH; the reaction product with polyvinyl alcohol of the ketone,

the latter being made by elimination of the elements of Water from tridecafiuoro-Z-methyl-Z-ethyl-1H,lH-butane l-carboxylic acid, (C 'F (CF )CCH COOH; and acrylic esters of the perfluorotertiary alcohols (C 1 COH and (C F (CF )COH. Further examples of these monomers include acrylic esters and methacrylic esters of highly fluorinated isopropyl alcohols such as s-hexafluoroisopropyl alcohol and perfluoroisopropyl alcohol and s-tetrafiuorodichloroisopropyl alcohol; and polymerisable derivatives of the perfluoroketones (CF CO, (C F CO, (C F )(OF )CO and of the highly fluorinatcd ketone (C F (CF )CCH COCF Other types of fiuorinated monomers having highly branched structures include polymerisable epoxide derivatives of perfluorotertiary alcohols such as wmamoornon-on,

and monomers in whose molecules the highly branched fluorine-bearing part is linked to the unsaturated polymerisable part by other groups, for example acrylic and methacrylic esters of the substituted alkanols R; CH OH where R, represents a branched perlluoroalkyl group and n is an integer equal to 2 or more.

Among highly fluorinated monomers in which the fluorine-bearing part is linear or substantially linear and which yield polymers suitable for the compositions of the invention are polymerisable derivatives of perfiuoroalkanoic and perfluorosulphonic acids containing 4 to 20, preferably 5 to carbon atoms in the chain, for example the vinyl esters of perfluorooctanoic acid, and of other acids, for example (CF )(CF Cl)OF(CF COOH and (CF CF(CF COOH; acrylic esters of omega-perfluoroalkyl-substituted alkanols where the C F group is linear and n is from 3 to about 12 and m is from 1 to about 12, for example CF (CF CH O CCH=CH 1H,1H pentadecafluorooctyl acrylate.

Tables 1-3 show the oil-repelling ratings of materials after treatment with various mixtures of the invention as determined by the method described in the Minnesota Mining and Manufacturing Companys publication 3M Textile Chemicals Appendix ATest Methods, page 1, and also described in UK specification No. 1,062,221, page 4, line 26, to page 5, line 11. The higher the rating number the greater the oil-repelling effect. Table 1 shows mixtures of the reaction product of polyvinyl alcohol and perfiuoroctanoic acid, referred to as A and having a linear structure, and the reaction product of polyvinyl alcohol and the highly branched fluorinated ketene gaberdine and wool gaberdine by padding to give a 1 to 2% pick-up of solids, and to suede leather by spraying.

TABLE 1.MIXTURES OF A AND B 1H,lH-pentadecafiuorooctyl acrylate, referred to as component X, and 90% by Weight of homopolymers, referred to as component Y, of respectively (i) the acrylic ester of perfiuoroisopropyl alcohol,

(CF 3 OFO CCH= CH (ii) the acrylic ester of s-hexafluoroisopropyl alcohol, (CF CHO CCH=CH (iii) the methacrylic ester (C 1 CF CCH CO CH CH O CC (CH :CH

of the monoethylene glycol ester (C 1 CF CCH CO CH CH OH of the acid (C F OF CCH COOH, that is to say tridecafluoro-2-methyl-2-ethyl-1H,lH-butane 1 carboxylic acid, (iv) the methacrylic ester C F OC H CH O CC (CH =CH of the tetrafiuoroethylene pentamer derivative C F OC H CH OH of p-hydroxybenzyl alcohol, (v) the vinyl ester (C F CF CCH CO CH=CH of tridecafiuoro 2 methyl-2-ethyl-1H,1H-butane-1-car- 5 0 boxylic acid.

TABLE 3 Oil-repelling ratln gs Gaberdine Mixtures 90% Y, 10% X by weight-Y Cotton Wool le a iz l t (i) [(CFs)2CFO2CCH=CH2]n 100 100 (ll) [(CF3)ZOHO2CCH=CH2L; 100 100 100 (iii) {(C2F5)2CFZCOH2C02CH2CH202CC(CH3) CH2]n 100 100 100 (iv) [CmFmDCeHqCHzOzCC (CH )=CH2]n 100 100 100 (v) ZF5 2OF3CCH2CO2CH=CI' 2]u 100 100 90 (C F (CF )CCH=C:O referred to as B. Table 2 shows mixtures of A and the polymer referred to as C, in which the C F part of the molecule is highly branched and derived from the oligomer 2 4)5- The mixtures were dissolved in 1,2,2-trifiuoro-l,1,2- trichloroethane to give solutions containing 2% by Table 4 shows the effect on the resistance to dry-cleaning and laundering operations that can be given by incorporating in mixtures of copolymers of highly branched monomers and copolymers or homopolymers of predominantly linear monomers minor proportions of monomers containing cross-linking sites in their molecules. Toluylene diisocyanate was used as such a monomer for copolymer mixtures containing hydroxyethyl methacrylate, and chloracetic acid for those containing methylol acrylamide.

weight/volume. The solutions were applied to cotton The various mixtures branched chain, 10% substantially linear chain molecules, by weight) were applied to cotton gaberdine as solutions in 1,1,l-trichloroethane, and the treated cloths cured at 150 C. and then evaluated for waterand oil-repellency. The treated cloths were then subjected to dry-cleaning and laundering cycles and again evaluated.

The dry-cleaning cycle comprised tumbling for 5 minutes in perchlorethylene at room temperature containing 2.25% soap and 0.15% water by weight.

The laundering cycle comprised agitation for 20 minutes at 70-80 C. in water containing 1% by weight of a proprietary washing powder based on inorganic polyphosphates and organic surface-active agents, drying and ironing.

-In Table 4 OR signifies oil-repelling rating determined as hereinbefore described, and WR signifies water spray rating determined as described in British standard specification No. 3702.

Also in Table 4 BMA signifies butyl methacrylate FOA signifies 1H,1H-pentadecafiuorooctyl acrylate HEMA signifies hydroxyethyl methacrylate VPC signifies vinyl ester of tridecafluoro-2-methyl-2-ethyl- 1H,1H-butane-l-carboxylic acid VPOB signifies vinyl ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzoic acid POBMA signifies methacrylic ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzyl alcohol C1OF1QOC6H4CH2O2CC MAM signifies N-methylol acrylamide.

(2) homopolymers of the glycidyl derivatives of any of the above alcohols,

(3) homopolymers of the vinyl esters of the acids having the formulae z 5)2(CF )C.CH COOH n oc mcoon kfoc mcn coon in which R is a branched perfluoroaliphatic group derived from branched oligomers of tetrafluoroethylene (4) homopolymer of vinyl alcohol esterified with the ketene (C F (CF )C.CH=C=O (5) and copolymers of any of the said homopolymers containing branched perfluorocarbon chains with non-fluorine-containing vinyl and acrylic ester monomer.

2. A polymeric composition as claimed in claim 1 in which incorporated in the copolymers are minor proportions of monomers containing cross-linking sites in their molecules.

3. A polymeric composition as claimed in claim 2 in which the monomers containing cross-linking sites in their molecules are selected from hydroxyethyl methacrylate, methylol acrylamide and glycidyl methacrylate.

4. A polymeric composition comprising (a) from 0.50% to 15% by weight of a homopolymer of 1H,1H- pentadecafluorooctyl acrylate and (b) from 85% to 99.5% by weight of a homopolymer of a monomer selected from (i) the methacrylic ester TABLE 4 After Initial dry After launproperties cleaning dering Branched chain component Linear chain component WR R WR OR WR OR (V PO plus BMA plus HEMAL. (FOAM 100 3 100 3 (FOA plus BMA plus HEMALJ 4 100 3 100 3 90 (V PC plus BMA plus MAM... (FOA) 5 100 3 90 4 100 (VPOB plus BMA plus HEMA) {FOA).. 6 100 3 80 4 80 FOA plus BMA plus HEMA)|1 4 100 2 3 (POBMA plus EMA plus HEMA)n. (FOA plus BMA plus HEMA).. 4 100 3 90 3 60 What we claim is: 1. A polymeric composition comprising (a) from 0.50% to 15% by weight of a fluorinated polymeric material selected from the group consisting of homopolymers of the vinyl esters of perfluoroalkanoic acids, and copolymers of the said esters with nonfluorine-containing vinyl and acrylic ester monomers, in all of which the perfiuoro part of the molecule is an unbranched aliphatic chain containing from 4 to 20 carbon atoms, and (b) from to 99.5 by weight of a fluorinated polymeric material selected from the group consisting of (1) homopolymers of the acrylates and methacrylates and epoxy containing derivatives of the alcohols having the formulae R OC H- CH 0H RfOCHzCHzOH where n is 2 or more in which R, is a branched perfluoroaliphatic group derived from branched oligomers of tetrafluoroethylene and of alcohols having the formulae of the tetrafluoroethylene pentamer derivative of p-hydroxybenzyl alcohol C F OC H CH OH, (ii) the vinyl ester C F OC H CO CH=CH of the tetrafluoroethylene pentamer derivative of p-hydroxybenzoic acid and (iii) the vinyl ester of tridecafluoro-2-methyl-2-ethyl- 1H,1H-butane-1-carboxylic acid,

( 2 5) 2 3 H CO CH CH 5. A polymeric composition comprising (a) from 0.50% to 15% by weight of a homopolymer of 1H,1H- pentadecafluorooctyl acrylate and (b) from 85 to 99.5% by weight of a copolymer of butyl methacrylate and a monomer selected from (i) the methacrylic ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzyl alcohol, (ii) the vinyl ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzoic acid and (iii) the vinyl ester of tridecafluoro-2-methyl-2-ethyllH,1H-butaue-1-carboxylic acid.

6. A polymeric composition comprising (a) from 0.50% to 15% by Weight of a copolymer of 1H,1I-I-pentadecafiuorooctyl acrylate and butyl rnethacrylate, and (b) from 85% to 99.5% by weight of a copolymer of butyl methacrylate and a monomer selected from (i) the methacrylic ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzyl alcohol, (ii) the vinyl ester of the tetrafluoroethylene pentamer derivative of p-hydroxybenzoic acid and (iii) the vinyl ester of tridecafluoro-2-methyl-2-ethyl-lH,lHbutane-1-carboxylic acid.

7. A polymeric composition as claimed in claim 6 in which at least one of the copolymers includes minor proportions of monomers containing cross-linking sites in their molecules and selected from hydroxyethyl methacrylate and methylol acrylamide.

8. A polymeric composition comprising (a) from 0.50% to 15% by weight of the reaction product of poly- (vinyl alcohol) and perfluorooctanoic acid and (b) 85% to 99.5% by weight of the reaction product of poly(vinyl alcohol) and the ketene (C F (CF )CCH=CO.

9. A polymeric composition comprising (a) from 0.50% to 15 by weight of the reaction product of poly- (vinyl alcohol) and perfluorooctanoic acid and (b) 85 to 99.5% by weight of the homopolymer of the vinyl ester of the tetrafiuoroethylene pentamer derivative of phydroxybenzoic acid.

10. A method of rendering textile fibres and leather References Cited UNITED STATES PATENTS 3,277,039 10/1966 Marascia et al 26029.6 3,256,230 6/1966 Johnson et a1. 26029.6 3,393,186 7/1968 Groves 260895 MURRAY TILLMAN, Primary Examiner C. I. SECCURO, Assistant Examiner US. Cl. X.R. 

